Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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TITLE OF THE INVENTION
METHO:D OF PRODUCING AQUEOUS DISPERSIONS AS A BASE FOR HOT
SEALING ADHESIVES
BACKGROUND OF THE INVENTION
Field of the Invention:
The present invention relates to aqueous dispersions based on poly(meth) acrylates,
produced in a multi-state emulsion polymerization process, and to the use of SUC]l dispersions
to prepare adhesives (bonding compositions) which are susceptible to hot-sealing.
Description of the Background:
In the l~ast, hot-sealing compositions have been devised for the packaging industry,
which compositions fully meet the applicable technical criteria, but which contain substantial
amounts of organic solvents. E.g., Eur. Pat. ] 29,178 describes a hot-sealable coating
composition comprised of a film-forrning dispersion of at least two different polymer types
with different adhesion properties in an organic solvent system, wherewith the dispersion
contains polymers of the two types and in addition contains a polymer comprised of units
corresponding to the two polymer types. Vinylidene chloride polymers have also been used
widely in the past as hot-sealable compositions.
Coating compositions for sealing metal substrates are of particular practical and
economic importance; in particular, compositions for providing seals between aluminum and
plastics such as polystyrene, polypropylene, and polyvinyl chloride, or between aluminum
and glass. (See Ullmann~ Enzyklopaedie der techn. Chemie, 6th Ed., 1985 ff., Vol 16, pub.
Verlag Chemie, pp. 101-103.)
Ger. Pat 4,209,651 (to BASF AG) describes an aqueous dispersion containing a
copolymer _ in the presence of which a polymerization is carried out to produce a copolymer
_. Copolymer A is produced by bulk polymerization, and is not a core-and-shell product.
The product materials are used in sealing PVC to paper board.
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Jap. Pat. 08-231729 A (Derwent No. 96-461419/46). The products comprise core-
and-shell polymers produced by emulsion polymerization followed by spray drying. The
shell has larger amounts of carboxyl-group-containing monomers which improve the re-
dispersibility of the product in water.
Rising awareness of environmental issues has created a trend away from solvent-
containing fonnulations and toward aqueous dispersions such that when, e.g., a coating or
adhesive is applied to a surface, organic compounds are not emitted into the environment.
Also significant is the trend away from chlorine-containing products, and, perhaps to a lesser
extent, aromatic compounds.
Technology has been able to adj ust, to some extent, to these more stringent
requirements. Thus, as disclosed in Ger. 29 06 1] 8, polymers of vinylidene chloride, used as
hot sealing adhesives, may be applied in the fonn of aqueous dispersions. In order to
improve adhesion to un-primed plastic and metal sheets, special "anchoring agents" may be
added to the composition. Suitable such additives are water-soluble polymers of functionally
substituted acrylamides and/or methacrylamides, or copolymers of these monomers with
acrylamide and/or methacrylamide, which (co)polymers are present as species dissolved in
the aqueous phase of the dispersion.
Two methods of coating of aluminum foils and sheets are in widespread use:
In the case of relatively aggressive filler materials, first a primer coat of about 2
microns in thickness is applied to the aluminum foil. This primer is comprised of a vinyl-
chloride-containing solution polymer. A finish coating comprised of a methacrylate resin of
4-8 micron thickness is then provided over the primer coat.
For cases of less aggressive filler materials, a single-coat system is used, employing a
hot-sealable coating of thickness of about 5- 10 microns comprising a mixture of the
abovementioned polymers.
Still unsolved is the problem of providing a non-chlorinated, hot-sealing adhesive in
the fonm of an aqueous dispersion with adequate adhesion. Ger. 27 27 914 (U.S. Pat.
4,291,090) and Ger. 28 55 147 disclose hot-sealing adhesives based on polyacrylate which
can be applied as aqueous dispersions. In some cases, these adhesives are not comprised
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exclusively of esters of (meth)acrylic acid. That is, they may contain one or more
comonomers, employed, e.g., for the purpose of modifying the melting temperature,
hardness, or adhesion properties of the adhesive. Suitable comonomers include, inter alia,
(meth)acrylamide, and aminoalkyl esters of acrylic acid and/or ofmethacrylic acid. The
specific effects which these comonomers have on the properties of the polymers is not
disclosed.
Ger. 39 30 743 (Can. Pat. App. 2,025,368.1) describes an aqueous polyacrylate
dispersion, which is useful as a hot-sealing adhesive, based on at least 70 wt.% of a
polyacrylate comprised of units of lower alkyl methacrylates and also containing polymerized
(meth)acrylamide or aminoalkyl (meth)acrylate. Other publications relate to aqueous
dispersions of copolymers of olefins and/or vinyl acetate, which copolymers contain units of
chlorinated monomers and are produced in a single-stage process. The described dispersions
exhibit poor adhesion to aluminum substrates.
Polymer dispersions, which are prepared from polymer particles having a core-and-
shell structure, which are described in the literature, either contain chlorinated monomers or
are not suitable for bonding plastics to aluminum.
Eur. Pat. 574,803 describes aqueous polymer dispersions of 5-80 wt.% of a copolymer
(A), having a glass transition temperature of 50-150 ~C, and 95-20 wt.% of a copolymer (B),
having a glass t:ransition temperature of -50 to +50 ~C, the two copolymers in the
composition havingwith a temperature difference of 20 ~C. There is no specif1c indication in
this publication that the proposed products are suitable for bonding plastics to aluminum.
Further, no appropriate two-coat methods are described in the cited state of the art
references.
A two-coat coating is proposed in Jap. Pat. App. 54-161,684 (Chem.Abstr.
92:199427x). I1irst, an aluminum foil is coated with the aqueous dispersion of a monomer
and then with a mixture of an ethylene-vinyl acetate copolymer, colophony, and wax, to a
thickness of 20 microns.
In connection with the object of formulating chlorine-free aqueous polymer
dispersions for use as hot-sealing adhesives, another problem exists which is the problem of
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compatibility with the state of the art apparatus employed. This problem is particularly
significant in the large-scale coating of aluminum foils and sheets. In particular, one should
be able to use customary methods of applying polymers as thin films (see PolymerHandbook, 2nd Ed., pub. Hanser Verlag), and the films employed should not be sticky at
ordinary temperatures.
A requirement imposed on means of hot sealing an adhesive to a suitable substrate is
that good adhesion for bonding the two materials (e.g. aluminum and polystyrene) must be
achieved in a short time and at temperatures which are not excessive and which are about,
e.g., 180-220~C.
The proposed packaging methods are also intended for used with foodstuffs. In such
applications, the monomers and the adjuvants must be selected such that the regulations
governing food packaging (German Federal Health Office guidelines BGA 14, and the
corresponding US FDA guidelines) are complied with.
In Ger. 39 30 743 an aqueous dispersion is proposed which has adequate adhesion to
an aluminum foil substrate coated with a vinyl chloride copolymer as a primer. Efforts to
modify such dispersions by incorporating units of adhesion-promoting monomers in order to
provide a variant which can be applied to un-primed aluminum have not been successful.
Thus the reference does not provide a solution to the problem of replacing chlorinated
primers. Other efforts using similar approaches, using polymers with simple particle
structures, have not been successful.
SUMMARY OF THE INVENTION
Accordingly, one object of the present invention is to provide an aqueous polymer
dispersion of improved hot-sealing and adhesion characteristics to plastic and metal
substrates.
Another object of the present invention is to provide aqueous poly(meth) acrylate
dispersions PD, which are produced by emulsion polymerization and which have at least a
two-stage particle structure, for use as hot-sealing adhesives.
Briefly, these objects and other objects of the present invention as hereinafter will
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become more readily apparent can be attained by aqueous poly(meth)acrylate dispersions,
comprising:
a particulate poly(meth)acrylate comprising the following components:
(A) 50-90 wt.% of methacrylic acid alkyl esters;
(B) 5-30 wt.% of an acrylic acid alkyl ester having a glass transition temperature
Tg in the range c. -20 to 50 ~C and having formula I:
o
CH2=CH--C--ORl ( FOrmul a I )
wherein R, represents an alkyl, aryl, or alkaryl group having 2-10 C atoms;
(C) 2-10 wt.% of a functionalized monomer of formula II:
IR2 R ' Formul a II)
CH2=C--C--OR3
wherein R2 represents hydrogen or methyl; and R 3 represents a glycidyl group
CH2--C\H /CH2
or an alkyl group which has 2-6 C atoms and is substituted with at least one hydroxyl group;
(D) 2-10 wt.% of at least one radical]y polymerizable carboxylic acid or a
polycarboxylic acid or a partially esterif ed polycarboxylic acid; and
(E) 0-40 wt.% of other monomers which are copolymerizable with (A) to (D);
wherewith, in the process of preparation, a first polymerization stage (Process Step 1 ) is
conducted with monomers of groups (A) to (C) and optionally (E), and in a secondpolymerization stage (Process Step 2), monomers of groups (A), (B), (D), and optionally (E)
are copolymerized; and wherewith the sum of the amounts of monomers (A) to (E) is 100
wt.%.
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The sum of the percentages of monomer units from groups (A) to (E) is 100 wt.%.
The preferred monomer of formula I is n-butyl acrylate. Preferred monomers of formula II
include glycidyl (meth)acrylate and hydroxyethyl (meth)acrylate.
Suitable monomers for group (E) monomers include styrene, (C, to C.~)-alkylstyrene
compounds, cycloalkyl (meth)acrylates, and the like. Data on glass transition temperatures
TG may be found in, e.g., Kirk and Othmer, 1978, "Encyclopedia of Chemical Technology",
3rd Ed., pub. J. Wiley, Vol. 1, pp. 387-389.
The ratio of the materials in the first po]ymerization stage to the masterials in the
second polymerization stage ranges from 30:70 to 70:30 parts by weight (pbw). A
recommended rule for the proportioning of the polymerization stages is that the amounts
should not differ by more than a factor of 2.5.
Additional preferred embodiments of the reaction include the following:
(i) The methacrylate content of the monomers polymerized in the first stage should be
about 60 + 20 wt.%.
(ii) The content of monomers of formula I in the monomers polymerized in the first
stage should be about 30 ~ 10 wt.%.
(iii) The content of monomers of formula II in the monomers polymerized in the first
stage should be about 10 ~ 5 wt.%.
(iv) The remainder of the monomers to complete 100 wt.% of the monomers in the
first stage is the monomer of group (E).
Still further preferences include:
(i) The content of methyl methacrylate and/or monomers of group (E) in the
monomers polymerized in the second stage should be c. 20 ~ 10 wt.%.
(ii) The content of (meth)acrylic acid in the monomers polymerized in the secondstage should be about 12 + 8 wt.%.
For each stage of polymerization, the sum of the percentages of all the monomers is
100 wt.%.
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The molecular weights of the poly(meth)acrylates in the dispersion PD are generally
in the range > 20,000 g/mol. The polymer content of the dispersions is generally in the range
20-65 wt.%; and the particle sizes are generally in the range 60-250 nm7 preferably 80-160
nm, particularly preferably 100-140 nm (deterrnined by photon correlation spectroscopy).
The poly(meth)acrylate dispersion PD of the invention is produced by emulsion
polymerization in the aqueous phase in the presence of anionic, cationic, or nonionic
emulsifiers, which emulsifiers are per se known, and in the presence of at least one radical-
fonning initiator, in a two-stage reaction (see Rauch-Puntigam, H., and Voelker, Th., 1967,
"Acryl- und Methacrylverbindungen", pub. Springer-Verlag, pp. 217-230).
It should be noted that certain advantageous properties, e.g. resistance to peeling, as
specified in food packaging regulations (BGA 14 guidelines, and the corresponding US FDA
guidelines), can be achieved with the use of additives.
The first stage may be conducted as a controlled-feed process: A suitable reaction
vessel equipped with a stirrer and heater is initially charged with deionized water and
emulsifier(s). Subsequently, after a certain temperature is reached, the initiator, preferably
dissolved in water, is added. The initiator may be, e.g., an inorganic peroxide such as
potassium peroxydisulfate (KPS) or ammonium peroxydisulfate (APS). It is recommended
that the content of initiator in the mixture at this point be in the neighborhood of 0.8 wt.%,
based on the weight of the monomers reacted in Process Step 1.
Suitable ionic emulsifiers, which are used in amounts of 0.01-2.0 wt.%, based on the
total weight of monomers, include anionic emulsifiers such as Aerosol OT75(R) of Cyanamid
BV and "Dowfax 2A1" of Dow Europa SA.
The addition of the above-described mixture for Process Step 1 is a controlled feed
over a prescribed period of time, e.g. 2 hr, in the first stage. As an example, the feed mixture
for Process Step 1 may comprise 20-60 wt.% of the total water to be used, plus the monomers
of groups (A) to (C) and optionally (E).
Advantageously, the mixture is then mixed for an additional period of time, e.g. 1 hr,
at elevated temperature, e.g. 80 ~C, following which it is allowed to cool, e.g. to 30 ~C. The
monomers described above in connection with "Process Step 2" are then added dropwise over
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a relatively short period of time, e.g. 30 min, and the mixture is then allowed to stand for an
appreciable period of time, e.g. 4 hr.
The resulting aqueous monomer/polymer mixture is then heated slightly, e.g. to 40
~C, and additional radical initiator, preferably a redox-type initiator, e.g. comprised of
peroxydisulfate, dithionite, and iron(II) sulfate, is added in water, and further polymerization
is initiated.
After the maximum temperature is reached, advantageously the temperature is
controlled, e.g. at 80 ~C, and the mixture is stinred for an additional period, e.g. 2 hr, to
complete the polymerization.
Altematively, the second stage can be canried out as another controlled-feed
"semicontinuous" step, with addition of a monomer emulsion gradually over a period of, e.g.,
2 hr.
The mixture is cooled to about 30 ~C, and advantageously a suitable preservative is
added, e.g. Acticid SPX(R) of Thor Chemie GmbH, along with a small amount of ammonia
(as 25% ammonia in water).
One may also add 0-5% of nonionic emulsifiers, e.g. ethoxylated alcohols, or
methacrylate esters of methoxypolyethylene glycols, e.g. "Carbowax 550", or alkylphenols,
and also an additional amount of an anionic emulsifier.
As a rule, the polymer dispersion (PD) may be used directly for coating. In certain
cases limited amounts of thickeners or film-fonning agents may be employed. The coating
may be applied by spraying, brushing, pouring, dipping, blade-coating, or roll-coating.
Generally the coating is applied in a thickness such that the dried coating has a thickness such
that the dried coating layer is 2-10 microns thick.
Advantageously, the coated articles are dried in a drying oven or by continuously
conveying the coated articles through a drying tunnel, possibly at reduced pressure and at
temperatures in the range 100-200 ~C.
In general, the higher the drying temperature, the shorter the drying time. Drying
times are, e.g., in the range 5 sec to 5 min. It is possible to apply the coating in multiple
coats. Preferably, the substrate to which the polymer dispersion (PD) is applied has a non-
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porous and continuous ("closed") surface, e.g. the surface of a plastic film or sheet, or
particularly of a metal foil or sheet, e.g. aluminum foil or iron.
As stated above, one advantage of using the present poly(meth)acrylate dispersions
(PD) as hot-sealing adhesives is that they solve the important and urgent problem of
formulating a hot-sealable composition based on an aqueous acrylate dispersion, e.g. the type
of dispersion disclosed in Ger. 39 30 74, which composition adheres strongly to substrates,
particularly metal foils or sheets, and in particular aluminum foils or sheets.
Accordingly, the principal embodiment of the present invention is hot-sealable coated
substrates, particularly of metal or plastic, coated with the present poly(meth)acrylate
dispersion(s) (PD) as a primer layer, with a second layer applied over the primer layer
comprised of an aqueous poly(meth)acrylate dispersion comprised of:
-- at least 70 wt.% of at least one Cl C4-alkyl ester of (meth)acrylic acid; and-- an appreciable amount of (meth)acrylamide and/or aminoalkyl (meth)acrylate;
wherewith the second layer is applied over the dried primer layer, and then dried.
For details beyond those provided in the example embodiments described below,
reference is made to the disclosure of Ger. 39 30 743. A representative such dispersion and
the means of its application are described hereinbelow (see Part II of the Example section).
In hot-sealing, the temperature in the coating must exceed the glass transition
temperature of the poly(meth) acrylate. The temperature of the hot contact members which
effect the sealing must exceed the required sea]ing temperature by an amount which increases
as the contact time is decreased and as the heat conduction through the substrate layer is
decreased. A thin metal foil has very good heat conduction, enabling the hot contact
members to be at a temperature which is only slightly above the melting temperature of the
poly(meth)acrylate. However, in practice the fastest possible sealing is desired, necessitating
substantially higher temperatures ofthe hot contact members, e.g. 120-220 ~C. In the case of
a plastic substrate, the hot contact member temperature may have to be limited because of the
glass transition temperature of the plastic. To obtain a seal of high strength, the pressure
exerted by the hot contact members should be at least 1 kp/cm2, preferably 3-6 kp/cm2.
The effective peeling resistance of hot-sealing samples from the Examples was tested
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in the customary fashion (sealing seam strength according to DIN 51 221).
The objective was to demonstrate that, e.g., the use of the present poly(meth)acrylate
dispersions as primers on aluminum foils or sheets, along with the use of the aqueous
dispersions of Ger. 39 30 743, as an outer hot-sealable layer provides adhesive properties
equivalent to those provided with primers based on solvent-containing and/or chlorinated
polymers.
Having now generally described the invention, a further understanding can be
obtained by reference to certain specific examples which are provided herein for pulpose of
illustration only and are not intended to be limiting unless otherwise specified.
The production and testing of hot-sealed samples is described hereinbelow, and atable of the strengths of the seals is be presented.
Comparative Examples:
To produce the comparative samples, a 10 wt.% solution of a commercial vinyl
chloride / vinyl acetate / maleic acid copolymer ("Vinylite VMHC", swpplied by Union
Carbide) in ethyl acetate was applied with a spiral blade applicator to a 40 micron thick soft
aluminum foil, in a thickness such that after drying 1 min at 180 ~C, a primer of thickness 2
micron was produced. The present poly(meth)acrylate dispersions (PD) were applied with a
blade applicator, and, to form a film, were immediately placed in a circulating air drying
cabinet preheated to 180 ~C before the water had evaporated from the dispersion coating.
The applicator was selected such that the layer of dried hot-sealable adhesive had thickness of
0.5-3.0 micron.
The poly(meth)acrylate dispersions of Ger. 39 30 743 can be applied by a similartechnique, after drying of the poly(meth)acrylate dispersions (PD).
The coated aluminum foils were sealed to polystyrene films and PVC films,
respectively, on edge regions 1 cm wide, using a laboratory-scale hot sealing apparatus
(manufactured by Brugger). The temperature of the hot contact members was 180 ~C, the
sealing pressure was 6 kp/cm2, and the sealing time was 1 sec.
Seal strength was measured by the procedure described in DIN 51 221 . The samples
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were first stored in a standard atmosphere (23 ''C, 50% relative humidity). Strips 15 mm
wide were cut transversely to the seal seam, folded outward, and tested in a tensile testing
machine, with one of the holding clamps gripping the free end of the aluminum foil and the
other gripping the free end of the plastic film, wherewith the tensile force was exerted
approximately transversely to the sealing seam on the test strip. The seal seam strength was
taken to be the force required to advance the separation of the foil and film to the extent of 15
mm.
To test water resistance of the seal seam, the sample strips were stored 48 hr in water
at room temperature, then tested for seal strength in the wet state by the above-described
method. Examples 1-20 (Table 1):
Ia. General method of producing poly(meth)acrylate dispersions PD with emulsion
polymerization:
Process variants:
(Iaa) Controlled feed ("semicontinuous") process.
(lab) Controlled feed followed by batch.
(lac) Controlled feed followed by controlled feed.
Into a round-bottom flask equipped with a stirrer, contact thermometer, and heater,
were charged deionized water and an emulsifier (Aerosol OT75(R)), and heating was begun.
After the temperature reached 90 ~C, ammonium peroxydisulfate (APS) dissolved in water
was added as an initiator, and Process Step 1 was begun.
(Iaa? For variant Iaa, the feed was added gradually over 240 min, followed by
stirring at 80 ~C for an additional 2 hr, to allow completion of the polymerization.
~ For variant Iab, the feed for Process Step l was added gradually over 120 min,
followed by stirring at 80 ~C for an additional 1 hr, and cooling at 30 ~C. Then the feed for
Process Step 2 was added dropwise over 30 min, following which the mixture was allowed to
stand 4 hr. The monomer/polymer mixture was then heated to 40 ~C and a redox initiator
was added. After the maximum temperature was reached, the temperature was maintained at
80 ~C and stirring was continued for an additional 2 hr, to allow completion of the
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polymerization.
~ For variant Iac, the feed for Process Step I was added gradually over 120 min,
followed by stirring at 80 ~C for an additional 40 min. Then the feed for Process Step 2 was
added gradually over 2 hr, following which the mixture was stirred for an additional 2 hr to
allow completion of the polymerization.
In all three variants (Iaa) to (Iac), a preservative in water was then added (for amounts,
see Table 3).
The data for Examples l-l9 are presented in Tables 1 and 3. Table l gives the
monomer compositions, amounts of emulsifier, and amounts of water, for Process Step I and
Process Step 2. Table 3 gives the amounts of various additives.
Ib. Production of the poly(meth)acrylate dispersions by emulsion polymerization in a
process comprising a batch process followed by a controlled feed process:
Into a round-bottom flask equipped with a stirrer, contact thermometer, and heater,
were charged the materials for the batch preparation (Process Step l). The monomer mixture
was the heated to 40 ~C and a redox-type initiator was added, to initiate the polymerization.
After the maximum temperature was reached, the temperature was maintained at 80 ~C and
stirring was continued for an additional 40 min. Then the feed for the controlled feed process
(Process Step 2) was added gradually over a period of 2 hr, following which the mixture was
stirred for an additional I hr to allow completion of the polymerization. The preservative was
then added at 30 ~C.
For example 20, Table 1 gives the monomer compositions, amounts of emulsifier, and
amounts of water, for Process Step 1 and Process Step 2, and Table 3 gives the amounts of
various additives.
II. Production of an aqueous polyacrylate dispersion (according to Ger. 39 30 743
"Coating for use as a sealant"):
In a 1-liter round-bottom flask equipped with a stirrer, contact thermometer, and
heater, 60 pbw of fully desalinated water and 0.05 pbw of sodium diisooctylsulfosuccinate
were heated to 80 ~C with stirring, and 2.4 pbw of a 10 wt.% solution of ammonium
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peroxydisulfate (APS) was added. Thereafter, the following were added dropwise over a
period of 4 hr, also at 80 ~C:
(i) An emulsion comprised of 240 pbw completely desalinated water, 4 pbw
sodium diisooctyl sulfosuccinate, l pbw APS, 320 pbw butyl methacrylate, 72 pbw methyl
methacrylate, and 8 pbw methacrylic acid amide, along with
(ii) A regulator comprising 0.4 g dodecyl mercaptan.
After another 2 hr at 80 ~C, the mixture was cooled to room temperature. A stable,
coagulate-free dispersion was obtained. The solids content was about 50 wt.%. Mean
particle diameter was 340 nm. The viscosity was 40 mPa-sec, as determined with aBrookfield viscosimeter.
III. Testing of the hot sealin~ properties:
For examples 1-20 (with Examples 1-3 being comparative examples), a coating 1.5
micron thick comprised of the respective poly(meth)acrylate dispersion (PD) was applied to
an untreated aluminum foil, followed by drying l min at 180 ~C. Then a coating 7 micron
thick comprised of the dispersion of Sec. II was applied, again followed by drying 1 min at
180 ~C. Strips 15 mm wide comprised of the thus treated aluminum foils were sealed against
a polystyrene film. Sealing duration was 1 sec, with the hot contact members being at 180
~C and exerting a pressure of 6 kp/cm2.
The adhesive strengths of these bonded structures are given in Table 4. If the bond
failed a hand separation test, the measurement was not performed. The first value of
resistance to peeling given is the value for the dry bond; the second is the value after storing
48 hr in water.
Results:
The results demonstrate that, by a rational selection of the monomers and the
production process, aqueous polymer dispersions of the invention can be produced which
yield primer layers on aluminum foil which primers provide adhesive properties equivalent to
those provided with primers based on solvent-containing and/or chlorinated polymers.
IV. Testing of adhesion of primers to various metallic substrates:
A variety of metal plates ("BM") comprised of aluminum or iron were cleaned with
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ethyl acetate. The dispersion being tested was applied to the desired site by means of a film
drawing apparatus, with gap heights of 20 micron, 80 micron, and 100 micron. Also,
dispersions to which 4% butyldiethylene glycol acetate ("BDGA") had been added were
applied, using gap heights of 100 micron and 200 micron. The adhesion was measured by a
grid-cutting test (with an a added Tesa film-peeling test), evaluated visually.
Results:
In all instances, the films adhered well.
Table 1 (parts 1 and 2 of 2):
Dispersions (PD) prepared according to variant methods Iaa, Iab, Iac, and Ib:
[For Table 1 parts 1 and 2, see 2 pages following the text.]
KEY to Table 1:
Columns:
(a) Process;
Examples 1-3 . (comparison examples). [Method variant] Iaa;
Examples 4-17. [Method variant] Iab, iirst process step is controlled feed process,
second process step is batch;
Examples 18-19. [Method variant] lab, first process step is controlled feed process,
and second process step is controlled feed process.
Examples 20. [Method variant] Ib [lit., "Iab"],
first process step is batch, and second process step is controlled feed process.Rows:
(b) First process step (controlled feed for Examples 1-19; batch for Example 20).
(c) VINYLITE VMHC = Vinyl Chloride/Vinyl Acetate/Maleic Acid Copolymer
(supplied by Union Carbide), dissolved in ethyl acetate.
-14-
Iaa Iaa Iaa Iab Iab lab Iab Iab Iab Iab
ProcessExample 1Example 2Example 3Example4Example 5Example 6 Example 7Example 8Example 9 Example 10
First StepSemicon- Semicon- Semicon- Semicon-Semicon- Semicon- Semicon- Semicon- Semicon- Semicon-
tinuous tinuous tinuous tinuoustinuous tinuous tinuous tinuous tinuous tinuous
Water 533.7 531 531 509.7 509.7 510.6 509.7 509.7 509.7 509.7
Aerosol 8.5 8.55 8.55 8.55 8.55 8.55 8.55 8.55 8.55 8.55
OT75(R)
Methyl 39.5 360 270 270 270 292.5 281.25 292.5 270
Methacrylate
Butyl Acrylate 35 135 135 135 135 135 ]35 135 135 135 D
Glycidyl 45
Methacrylate ~O
Hydroxyethyl 45 45 45 45 22.5 33.75 22.5 45
Acrylate
Butyl 697.5 ~
Methacrylate ~
Methacrylamide 18
Methacrylic22.5
Acid
Acrylic Acid22.5 45 45
Butyl 315 315
Methacrylate
-15-
Iaa Iaa Iaa Iab Iab Iab lab lab lab lab
ProcessExample 1Example 2Example 3Example 4 Example 5Example 6Example 7Example 8Example 9 Example 10
First StepSemicon- Semicon- Semicon- Semicon- Semicon- Semicon- Semicon- Semicon- Semicon- Semicon-
tinuous tinuous tinuous tinuous tinuous tinuous tinuous tinuous tinuous tinuous
Styrene 360
Dodecyl 0.45
Mercaptan
Second Step Example Example Example Example Example Example Example
Butyl 315 315 315 315 315 315 315
Methacrylate D
Methyl 90 90 112.5 101.25 90 112.5 ~
Methacrylate ~~
Acrylic Acid 45 45 45 22.5 33 75 45 22.5
Styrene 90
Polycarboxylic ~
Acld ~"
Aerosol
OT75(R)
Water
Ammonium
Peroxydisulfate
*Polycarboxylic Acid - Rohagit SL 140
-16-
Table 1: (Continued) Dispersions PD Prepared According to Variant Methods laa, Iab, lac, and Ib:
Iab Iab Iab Iab Iab Iab lab lab Iab Ib
ProcessExample ExampleExampleExample 14Example 15Example 16Example 17 Example 18Example 19 Example 20
11 12 13
First StepSemicon-Semicon-Semicon- Semicon- Semicon- Semicon- Semicon- Semicon- Semicon- Semicon-
tinuous tinuoustinuous tinuous tinuous tinuous tinuous tinuous tinuous tinuous
Water 482 2 482 2 482.2 482.2 814.3 482.2 370.4 266.9 361.5 629.2
Aerosol 8.55 8.55 8.55 8.55 3.43 8.55 10.3 4.28 3 0.9
Methyl 270 270 270 270 198 270 324 270 270 270
Methacrylate
Butyl Acrylate 135 135 135 135 54 135 162 135 135 135 , .
Glycidyl
Methacrylate
Hydroxyethyl 45 45 45 45 18 45 54 45 45 45
Acrylate
Butyl
Methacrylate ~"
Methacrylamide
Methacrylic
Acid
Acrylic Acid
Butyl
Methacrylate
Styrene
Iab Iab Iab Iab Iab Iab lab Iab Iab Ib
Process Example ExampleExampleE~xample 14Example 15Example 16 Example 17Example 18Example 19 Example 20
I l 12 13
FirstStep Semicon- Semicon-Semicon- Semicon- Semicon- Semicon- Semicon- Semicon- Semicon- Semicon-
tinuous tinuoustinuous tinuous tinuous tinuous tinuous tinuous tinuous tinuous
Dodecyl
Mercaptan
Second StepExampleExampleExample Example Example Example Example Semicon- Semicon- Semicon-
tlnuous tmuous tmuous
Butyl 315 315 315 315 126 315 378 315 315 315
Methacrylate D
Methyl 90 90 36 90 108 90 o
Methacrylate ,.
Acrylic Acid45 45 45 45 18 54 45 45 45 u,
Styrene 90 90 90 90
Polycarboxylic 112.5
Acid O
Aerosol 4.28 3 7.88
Water 266.9 261.5 210 4
~ 09 0.9 0.9
Ammomum
Peroxydisulfate
*Polycarboxylic Acid - Rohagit SL 140
Table 2: Amounts of Additives
Initial Charge to Reactor Second Process Step (but first process step in Example 20) After Polymerization
Water AerosolAmmonium Ammonium Fe2(SO4)3bNa2S2OsC Sodium Acticid SPXNH
OT75(R)Peroxydisulfatea Peroxydisulfatea Hydroxymethyl in 10gwater
340 0.255 2.7 1.80.34
2 340 0.225 2.7 1.80.34
3 340 0.225 2.7 1.80.34
4 340 0.225 2.7 0.72 0.0009 0.36 1.80.34
340 0.225 2.7 0.72 0.0009 0.36 1.80.34
6 340 0.225 2.7 0.72 0.0009 0.36 1.80.34
7 340 0.225 2.7 0.72 0.0009 0.36 1.80.34
8 340 0.225 2.7 0.72 0.0009 0.36 1.80.34
9 340 0.225 2.7 0.72 0.0009 0.36 1.80.34
340 0.225 2.7 0.72 0.0009 0.36 1.80.34
11 340 0.045 2.7 0.72 0.009 0.504 1.80.34
12 340 1.8 2.7 0.72 0.009 0.504 1.80.34
13 340 0.045 2.7 0.72 0.009 0.504 1.80.34
_19_
Initial Charge to Reactor Second Process Step (but first process step in Example 20) After Polymerization
Example
Water AerosolAmmonium Ammonium Fe2(SO4)3b Na2S2OsCSodium Acticid SPX NH3e
OT75(R)Peroxydisulfatea Peroxydisulfatea Hydroxymethyl in 10g water
Sulfinated
14 340 1.8 2.7 0.72 0.009 0.504 1.8 0.34
556 0.091 1.08 0.288 0.0043 0.202 0.72 0.135
16 340 0.225 2.7 0.72 0.009 0.504 1.8 0.34
17 268 0.27 3.24 0.864 0.011 0.605 2.16 0.41
18 340 0.225 2.7 1.8 0.34 ~
. .
19 340 0.3 0.9 1.8 0.34 ~
0.72 0.009 0.504 l.~ 0.34 1-
aAmmonium Peroxydisulfate dissolved in 20g water O
bFe2(SO4)3 dissolved in 10g water
CNa2S2O5 dissolved in 20g water
dSodium Hydroxymethyl Sulfinate dissolved in 20g water
e20% Ammonia in 5g water
-20-
CA 022309~1 1998-03-03
Table 4: Measurements of resistance to peeling:
Example Peeling Strength, N, for 15 mm strip width:
Number Seal between aluminum and Seal between aluminum and PVC
polystyrene ("PS")
Normal pressed After 48 hr in Normal Pressed After 48 hr in
w ater water
Value too low
2 4.8 1.7 2.1 1.]
3 5.7 3.7 3.1 1.7
4 6.9 8.0 6.7 5.8
8.1 4.3 5.1 2.5
6 7.0 6.0 3.8 2.4
7Value too low
8Value too low
9Value too low
10Value too low
11 6.9 4.7 3.4 2.9
12 5.0 6.2 3.3 3.3
13 4.7 2.3 2.3 2.3
14 7.6 7.4 4.8 3.7
4.2 6.8 1.9 2.4
16 4.2 4.9 1.9 2.1
17 5.9 1.9 3.9 2.9
18 2.0 0.6 1.3 0.7
19 8.1 8.0 6.9 5.6
3.8 4.3 2.4 2.6
Table 5: Results of adhesion tests of Example 9 sample, using grid-cutting test.(Data are the number of fields loosened in the test.)
Film according to Example l9Film according to Example 19 + 4%
butyldiethylene glycol acetate
("BDGA"), applied to solid metal plates
("BM")
Drying 180~C, 1 minute; Drying 180~C, 2 minutes; Drying 180~C, 1 Drying 180~C, 2
applicationwith film-drawing applicationwith film-drawing minute; application minutes;
apparatus; column headings areapparatus; column headings are with film-drawing application with ~,
gap height (micron) gap height (micron) apparatus; column film-drawing D
headings are gap apparatus; column
height (micron) headings are gap ',
height (micron)
20 ~m 60 llm 100 llm 20 llm 60 llm 100 ~m 100 llm 200 ~m 100 !lm 200 ~m
Actual coating thickness o
(micron) (measured on the O
Fe plate) 12-19 14-28 15-27 14-18 13-17 12-33 15-28 33-46 20-30 -40
Iron plate 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 o/o
Aluminum plate 2/4)*** 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0
***Drying was not optimal for this [failing] test.
CA 022309~1 1998-03-03
German priority application 197 08 412.5 filed March 3, 1997 is hereby incorporated
by reference into the present application.
Obviously, numerous modifications and variations of the present invention are
possible in light of the above teachings. It is therefore to be understood that within the scope
of the appended claims, the invention may be practiced otherwise than as specifically
described herein.
-23-
